Process for breaking petroleum emulsions



Patented May 15, 1951 PROCESS FOR BREAKING PETROLEUM EMULSIONS Melvin De Groote, St. Louis, Mo., assignor to Petrolite Corporation, Ltd., Wilmington, DeL, acorporation of Delaware No Drawing. Application July 28, 1949, Serial No. 107,381

8 Claims. (Cl. 252-344) This invention relates to processes or procedures particularly adapted for preventing, breaking or resolving emulsions of the water-inoil type, and particularly petroleum emulsions.

Complementary to the above aspect of the invention herein disclosed is my companion invention concerned with the new chemical products or compounds used as the demulsiiying agents in said aforementioned processes or procedures, as well as the application of such chemical products, compounds, or the like, in various. other arts and industries, along with the method for manufacturing said new chemical products or compounds which are of outstanding value in demulsification. See my cO-pending application, Serial No. 107,382 filedJuly '28, 1949.

My invention provides an economical and rapid process for resolving petroleum emu'sions of the ditions just mentioned are ,of significant .value in removing impurities, Particularly inorganic salts, from pipeline oil.

Demulsification as contemplated .inthepresent application includes the preventive .step .of .commingling the demulsifier with the aqueous component which would or might subsequently become either phase of .the, emulsion in the absence of such precautionary measure. Similarly, such demulsifier may be mixed with the hydrocarbon .o mnonent- .In my co-pending applications, Serial Nos. 104,801, 104,802, .10l,803,.and-,104,804, .allfiledJuly 1d, 1949, ,I have described the breaking of petroleum emulsions by ,means vof certain polyol A ethers. ,Said inventions, or invention, -described in the aforementioned .co-pending applicatiql s may, in the broadest aspect, ,loe considered ,as being concerned with a ,process .for breaking petroleum emulsions of the -waterineoil ype characterized by subjecting theemulsion the action of a. demulsifier ,incl ld t-ighighmolal oxyp opy a o d v tives of monom r c :Dfllllhldli compounds with-the proviso that (a) the initial l y reactant behest-re en i adica-l having at least '8 uninterrupted carbon atoms; -(b) the initia -po 1yhyd c react n hav a 1 molecular .yvei ht no-tlover 1200 andsat least fl-lfrydroxyl raditale; t e ini ia s l hvdri r ..so b e-a d xvlen e nspluble; .ei) thee y mpyl ntibewatertion end product be water-insqll ile.allddiyleneterial.

soluble; .(e) the oxypropylation end product be within themolecularweightrange of 2000 $030,000 on .an average statistical basis; (I) the solubility characteristics of the oxypropylation end product in respect to water and xylene be substantially the result of the oxypropylation step; (9) the ratioof propylene oxide per hydroxyl in the initial polyhydric reactant be within the range of 7 to '70; (h) the initial polyhydric reactant represent not more than 12 /2% by weight of the oxypropylation end product on a statistical basis, and (i) the preceding provisos being based on complete reaction involving the propylene oxide and the initial polyhydric reactant.

The present invention i somewhat akinto the aforementioned invention, or inventions, insofar that it invo ves also a high molal polyo obtained by the ction of pro ylene oxide but containing in addition basic nitrogen atoms. Stated another way, in the present invention the initial material employed, instead of being a carbohydrate as exemplified by mannitol, sorbitol, sorbitan, etc., is a polyamine or an oxyalkvlated derivative thereof, such as diethylene triamine, triethylene tetramine, or tetraethylene pentamine, or compounds which bear a simple genetic relationship thereto without any basic change in the structure as, for examp e, the glycide derivatives of such amines, and ethylene oxide derivatives of such amines, the low molal acyl derivatives of such amines, the low molal alkyl derivatives of such amines, etc. It is also obvious that there isanother difierence between initial reactants of the present invention and the initial reactants employed as raw materials in the above mentioned co-pending applications, i. e., Serial Nos. 104,801, 104,802, 104,803, and 104,804, all filed July 14, 1949. This difference is .the fact that the raw materials herein employed may be .reactive towards propylene oxide by virtue of an amino hydrogen atom as distinguished from a labile hydrogen atom attached to an oxygen atom as in the case of sorbitol, sorbitan, etc.

It is also practical to have initial raw materials suitable for use in the instant invention in which the molecular weight is somewhat higher than in the case of the polyhydric alcohol'type of ma- These differences will become obvious in the subsequent description of the present invention.

Summarizing what has been said, the present invention in its broadest aspect is concerned with a process for breaking petroleum emulsions of the water-in-oil type characterized, by subjecting the emulsion to the'action of a demulsifier including high molal oxypropylation derivatives of monomeric polyamino compounds with the proviso that (a) the initial polyamino reactant be free-from any radical having at least 8 uninterrupted carbon atoms; (b) the initial .polyamino reactant havea molecular weight .of not over 1800 and at least a plurality of reactive hydrogen atoms; the initial polyamino reactant must be Watersoluble; (d) the oxypropylation end product must be water-insoluble; (e) the oxyprop end product be within the molecular weight ra g of 2000 to 30,000 on an average statistical basis; oxypropylatlon end product in respect to water must be substantially the result of the oxypropylation step; (g) the ratio of propylene oxide per initial reactive hydrogen atom must be within the range of 7 to 70; (h) the initial polyamino reactant must represent not more than by weight of the oxypropylation end product on a statistical basis; (1') the preceding provisos are based on the assumption of complete reaction involving the propylene oxide and initial polyamino reactant; (9') the polyamino reactant must contain at least one basic nitrogen atom; and (k) the nitrogen atoms are linked by a carbon atom chain.

Reference to basic nitrogen atom refers to one which is not attached to a negative group such as aryl or acyl. Phenylethylenediamine or acetylethylenediamine both qualify as polyamines for the purpose of this description.

In the foregoing summarization of the invention in its various aspects and in the claims reference to monomeric is not intended to exclude compounds such as diethylene triamine, triethylene tetramine, or tetraethylene pentamine but is intended to differentiate from linear polymers or dimers, or other higher polymeric types, obtained, for example, by reaction between a dicarboxy acid, such as adipic acid, and tetraethylene pentamine, or the like.

Briefly stated, the present invention is concerned with breaking petroleum emulsions by means of certain polyol ethers of certain hereinafter specified polyamino compounds as exemplified by diethylene triamine, triethylene tetramine, and tetraethylene pentamine. The preparation of such oxypropylation derivatives is described hereinafter in detail. Such ethers are obtained by treating a water-soluble polyamino reactant having a plurality of functional groups (hydrogen atoms attached to oxygen or nitrogen so as to be reactive toward an alkylene oxide) with propylene oxide. A plurality of propylene oxide is used in molal proportion to the polyamino reactant so as to convert the initial waterso-luble product into an ultimate resultant which is water-insoluble.

For instance, the herein described resultants, or more correctly products of reaction since they invariably and inevitably represent cogeneric mixtures rather than a single component, when mixed with distilled water so as to give a 5% solution, suspend after a fashion during vigorous agitation but on being allowed to stand in a quiescent stage immediately separate out so that within a short length of time, for instance, within a few minutes to several hours, all or substantially all the big bulk of material has separated from the aqueous solution or suspension. In fact, in the higher stages of oxypropylation the materials obtained seem to go into water at room temperature with considerable difiiculty and if the water happens to be warm, for instance, at a temperature of or '70 0., the materials are even less soluble. An example of a product difiicult to disperse even with vigorous shaking and which, even so, does not stay dispersed, is the resultant obtained by treating one mole of tetraethylene pentamine with 200 moles of propylene (f) the solubility characteristics of the 4 I oxide. Reference as to solubility is in ordinary cold water at approximately room temperature, for instance, 225 C:, or thereabouts.

For convenience, what is said hereinafter is divided into three parts. Part 1 is concerned with the description of the polyamino reactants employed, as well as reference to other compounds, products, etc., so there may be a clear line of demarcation between the present invention and what may appear elsewhere. Part 2 is concerned with the preparation of the oxypropylated derivatives, and Part 3 is concerned with t1 e use of an oxypropylated derivative as a demulsifier for petroleum emulsions of the Water-in-oil type.

PART 1 In the present invention the initial reactants are characterized by certain features which have been pointed out in some detail previously. Suitable reactants are exemplified by three compounds which have been mentioned previously, that is, diethylene triamine, triethylene tetramine, and tetraethylene pentamine. The higher polyamines in this series are equally satisfactory, such as pentaethylene hexamine, hexaethylene heptamine, heptaethylene octamine, etc. In some instances the carbon atom chain uniting two nitrogen atoms may, itself, be substituted by the presence of a hydroxyl radical or a ketonic oxygen atom, or a methyl radical. It is preferable that the polyamino compound has at least two basic nitrogen atoms and at least 4 reactive hydrogen atoms. As has been stated previously there are any one of a number of compounds derived from polyamines bearing a simple genetic relationship to such amines which are just as satisfactory for use as initial reactants.

For instance, the polyamine can be treated with ethylene oxide, glycide, butylene oxide, methyl glycide, or a combination of such oxyalkylating agents; or such polyamine can be treated with some propylene oxide and one or more of the oxyalkylating agents previously mentioned. Needless to say, if such an amine is treated with propylene oxide at an initial stage, such product need not be considered as the initial reactant but the amine itself may be so considered. One could produce either salts or amides of low molal acids, such as acetic acid, formic acid, hydroxyacetic acid, lactic acid, and the like; or the ultimate final product can be converted into a salt by reaction with these acids, or by reaction with inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, etc. One can introduce readily low molal acyl radicals as stated, or

'alkyl radicals, by use of conventional alkylating agents such as dimethyl sulfate, etc. Ether radicals can be introduced in the usual manner. However, all such derivatives are characterized by the fact that they still meet all the requirements set forth elsewhere as to water-solubility, presence of reactive hydrogen atoms, presence of basic nitrogen atoms, etc., and thus obviously bear a simple genetic relationship to the initial polyamino compound.

The polyamines are obtained in various manners, such as reaction involving ethylene dichloride, propylene dichloride, butylene dichloride, or the like, with ammonia, or other amines. Note particularly the amines described in the following patents: U. S. Patents Nos.'2,049,467, dated August 4, 1936, to Mnookin; 1,952,008, dated March 20, 1934, to Bruson; 1,951,992, dated March 20, 1934, to Perkins; and 2,291,396, dated July 28,1942, to Lieber.

' atria-mo 011.1161 methods involve hydrogenation proce- .dures. See U. S. Patents Nos. 2,317,757, dated April27, 1943, to .Graf 2,408,172, dated September .24. 194.6, to Johnson; 2,318,729, dated May 11 1943, to Wilson; and 2,364,178, dated December .1944. to Wilson.

In some instances amineshaving 10, 12, or basic nitrogen atoms are obtained by merely treating amines of the type described elsewhere, .such as the polyethylene amines of ethylene .imine. In a few cases an unsaturated group may be present; see U. S. Patents "No. 2,440,724 dated May 4, 1948,1130 Morey, and 2,441,659, dated May 318, 19.48, :to Morey.

In some cases amines which oth rwi e qualify.

exc pt the matter of wat r-s l ihty. m y be treated with one of :the alkylene oxide previously mentioned which is ethylene oxide, or ,glycide, or with ethylene imine or a combination so as to yield a suitable initial raw material. See, ;for instance, the table found on page 2 of U. S. Patent No. 2,393,825, dated January 29, 1946, to Senkus. See also certain amines described in U. S. Patent No. 2,262,357, dated November 11, 1941, to De Groote. Note the suitable amines depicted and described in U. S. Patent No. 2,391,- .830, dated December 25, 1945, to Jayne et al., which include, among others, the following: Hyv,droxy ethyl ethylene diamine; l,2-di-(2'-ethanolamino) -ethane; 1,2 4 di (2',3'-propan-diol-amino) ethane; 1,3-di- (2'-.ethanolamino) -2-propanol; N-1,2'-diamino propylamino 2 ethanol;

;1,2-, di -(e thanolamino) 3 aminopropane; 1,2,3-

tri-(ethanolamino) -propane; tri- (mono-methylamino-methyD-ethanol; and 1,2- di l(4 cycl o hexanolamino) -.ethane.

Other suitable amines are described in U. .8. Patent No. 2,046,720, dated July 7, 1936, to Bottoms, which were .the following: N-(2-hydroXy-3- amino propy1)-ethylene diamine-1,2; N.-dimethyl-N- (2-hydroxy-3-amino propyl) -ethylene diamine 1,2; N-N'-diethyl-N'-(2-hydroxy-3-amino propyD-ethylene diamine-1,2; N-(2-hydroxy-3- amino propyl) -N-(2,3-dihydroxy 4 aminobu- .tyl) ethylene diamine 1,2; N (2 hydroxy-3- amino propyl) -2-hydroxy propylenediamine-1,3 and N;N'-di(Z-hydroxy-3-amino propyl)2-hydroxyl propylene diamine-1,3.

'Where propylene or butylene dichloride is used for reaction with ammonia to yield amines, the chlorine atoms may be attached to two adjacent carbon atoms. The result is that such amines have a carbon atom chain substituted bya methyl or ethyl group. 'Where glycerol monochlorohydrin, or glycerol dichlorohydrin, is used for reaction with ammonia or the like to produce amines, one or more carbon atoms may be substituted by a hydroxyl radical. Similarly, a carbon atom may have an oxygen atom attached thereto. Reference is made to U. S. Patent No. 2,262,358, dated November 11, 1941, to De Groote. Note the description of the following amines:

(See German Patent No. 635,904, to I. G. Farbenindustrie, A.-G., dated October 1, 1946.)

N,N' di(2-hydroxy.-3earninopropyl) -2-hydroxy propylene diamine-1,3.

A variety of other suitable amines aredescribed in the following patents: U. S. Patent No. 2,048,- ,990, dated July 28, 1936, to Britton et al.; U. S. Patent No. 2,149,273, dated March 7, 1939, to Carothers; U. S. Patent No. 1,790,042, dated/January 27, 1931, to Eisleb; U. S. Patent No. 2,246,- .524, .datedJune 24, 1941, .to Kyrides; U. S. Patent No. 2,368,521, dated January 30, 1945, to Clifford, ,et al.; and U. S. Patent No. 2,368,968,..dated Feb.- ruary .6, 1945, to .Christmann.

As to the preparation of a variety .of suitable polyamines using ethylene imine, see US. Patent No. 2,318,729,.dated May ,11, 1943, to Wilson.

PART 2 The ox-ypropylation procedure employed in .the preparation of derivatives from polyamino reactants has been uniformly the same, particularly in the light of the fact that a continuous operating procedure was employed. In this particular procedure the autoclave was a conven- :tional autoclave, made of stainless steel and having a capacity of approximately one gallon, and a Working pressure of 1,000 pounds gauge pres- .sure. The autoclave was equipped with the conventional devices and openings, such as the variable stirrer operating at speeds from 50 R. P. M. to 500 R. P. M., thermometer well and thermocouple for mechanical thermometer; emptying outlet; pressuregauge; manual vent line; charge 'hole for initial reactants; at least one connection for conducting the incoming alkylene oxide, such as propylene oxide, to the bottom of the auto,- clave; along with suitable devices for both cool.- ing and heating the autoclave, such as a cooling jacket and, preferably, coils in addition thereto, with the jacket so arranged that it is suitable for heating with steam or cooling with water, and further equipped with electrical heating devices. Such autoclaves are, of course, in essence small scale replicas of the usual conventional autoclave used in oxyalkylation procedures.

Continuous operation, or substantially continuous operation, is achieved by the use .of a separate container to hold the alkylene oxide being employed, particularly propylene oxide. The container consists essentially of a laboratory bomb havinga capacity of about one-half gallon, or somewhat in excess thereof. This bomb was equipped, also, with an inlet .for charging, and an outlet tube going to the bottom of the containerso as .to permitdischarging of alkylene oxide in the liquid phase to the autoclave. Other conventional equipmentc n ists-Qf .c urse of the rupture disc, pressure gauge, sight feed glass, thermometer connection for nitrogen for pressuring bomb, etc. The bomb was placed on a scale during use and the connections between the bomb and the autoclave were flexible stainless hose or tubing so that continuous weighings could be made without breaking or making any connections. This also applied to the nitrogen line, which was used to pressure the bomb reservoir. To the extent that it was required, any other usual conventional procedure or addition which provided greater safety was used, of course, such as safety glass, protective screens, etc.

With this particular arrangement practically all oxypropylations became uniform in that the reaction temperature could be held within a few degrees of any point selected in this particular range, for instance, in most cases I have selected a point of approximately 160 to 165 C., as being particularly desirable and stayed within the range of 155 to 180 almost invariably. The propylene oxide was forced in by means of nitrogen pressure as rapidly as it was absorbed, as indicated by the pressure gauge in the autoclave. In case the reaction slowed up so the temperature dropped much below the selected point of reaction, for instance, 160 C., then all that was required was that either cooling water was cut down or steam was employed, or the addition of propylene oxide speeded up, or electric heat used in addition to the steam, in order that the reaction procedures at or near the selected temperatures be maintained.

Inversely, if the reaction proceeded too fast the amount of reactant being added, i. e., propylene oxide, was cut down or electrical heat was cut off, or steam was reduced, or if need be, cooling water was run through both the jacket and the cooling coil. All these operations, of course, are dependent on the required number of conventional gauges, check valves, etc., and the entire equipment, as has been pointed out, is conventional and, as far as I am aware, can be furnished by at least two firms who specialize in the manufacture of this kind of equipment. As an illustration of such oxypropylation procedure the following examples are included.

Example A The polyamino reactant employed was tetraethylene pentamine. This material is available as an amber colored liquid. In the oxypropylation of polyamino compounds having one or more basic nitrogen atom it is not necessary, at least in the early stage, to add an alkline catalyst such as sodium methylate, caustic soda, caustic potash, etc. In fact, the reaction takes place with comparative speed as illustrated by the initial step of oxyproplyation.

In this experiment 379 grams of tetraethylenepentamine were placed in the autoclave after flushing out with nitrogen. The bomb reservoir served as a holder for propylene oxide (which has been described previously) and was charged with more than 1800 grams of propylene oxide so that 1740 grams could be withdrawn by difference and noted on the scale. It is inconvenient to attempt to withdraw all the propylene oxide from the bomb reservoir for the reason that the exit tube does not go to the very bottom of the bomb. In this particular experiment the stirring speed employed was approximately 300 R. P. M. The temperature in the autoclave was raised to 150 C. before any oxide was added. In the instant series of experiments the products were invariably liquids and there was no difficulty in subsequent steps if the addition of sodium methylate was required as stirring would distribute or dissolve the catalyst. Before starting the experiment a range of to 180 C. was selected. Subsequent control of valves, reactor inlet, cooling water, steam, etc., are intended to keep the experiment within this range. When the temperature reached 150 C., and the catalyst was thoroughly dissolved as noted, propylene oxide was forced in using nitrogen pressure on the reservoir bomb. The pressure during the addition of the propylene oxide stayed comparatively low for the reason that the reaction was instant and there was no opportunity for unreacted propylene oxide to heat up and show pressure. The actual gauge pressure was approximately 55 pounds, or less.

The nitrogen pressure on the propylene oxide reservoir was 100 pounds which meant that due to the conventional check gauge arrangement propylene oxide could not be forced into the autoclave for reaction if at any time the pressure in the reactor moved about 100 pounds gauge pressure. In actual operation the 1740 grams of propylene oxide were added in approximately hour and at no time did the pressure go higher than 55 pounds, and the reaction operated smoothly; at no time did it go past the preselected maximum point at 180 C'. The bulk of the reaction took place at a range of ,to C. It will be noted that the amount of propylene oxide added was approximately 15 moles of propylene oxide for each mole of tetraethylenepentamine; or, stated another way, 2.5 moles of propylene oxide for each reactive hydrogen atom. This product stillshowed water-solue bility. The product was prepared essentially to be used as an intermediate product for further oxypropylation, as described in subsequent steps.

Example B 530 grams of the intermediate described in Example A, preceding (representing approximately 95 grams of tetraethylenepentamine and 435 gram of propylene oxide) were reacted with 1160 grams of propylene oxide without the addition of an catalyst. For practical purposes the operating conditions as to pressure, temperature, etc., were the same as in Example A, preceding. Since no catalyst was added and since alkalinity had been reduced the time required was somewhat longer, approximately 2 hours. This particular product represented a molal range of 55 moles of propylene oxide per mole of tetraethylenepentamine, or approximately 8 moles of propylene oxide per reactive hydrogen atom. The final product obtained represented 95 grams of tetraethylenepentamine plus 1595 grams of propylene oxide. The molecular weight was in the neighborhood of 3400.

Example C The initial reactant was 845 grams of the intermediate of Example B, immediately preceding. This represented 47.5 grams of tetraethylenepentamine, and 798 grams of propylene oxide. This polyamino reactant was combined with 1160 grams of propylene oxide, after adding 25 grams of sodium methylate as a catalyst. Note that no catalyst was added until this third stage. There would have been no objection, of course, to adding some catalyst to the second stage to speed up the reaction, if required.

The conditions of operation were substantially aseaeecr the same as in Example A, preceding. The end;

product in this instanceshowed distinct waterinsolubility. It, is to be noted that this particular product represented a. molal ratio of approximately 135 moles of propylene oxide per mole of tetraethylenepentainine, or approximately 19 moles of propylene oxide per reactive hydro- Example D' The initial reactant was 1,000 grams. of Example C, preceding. This represented, a little less than 24 grams of tetraethylenepentamine and. a little more than $76 grams of propylene oxide. Noadditional catalyst was added but thisv product was treated with 580 grams of propylene oxide under substantially the sameconditicns as noted in Example A, preceding. Propylene oxide was added in 1 hours.

This product yielded 1580 grams of the material in which the molal ratio of propylene oxide to polyamine was 215 to 1, and represented approximately 24 grams of tetraethyl'enepentamirre and 1556 grams of propylene oxide.

Example E The previous example, Example D, was split in two again .and one-half the sample; or 790 grams, were treated" with 4 moles of propylene oxide, or 2.32 grams. The initial. sample repre-e sented 12 grams of tetraethylenepentamine and 778' grams of propylene-oxide. SgrarnSof'sodium lt will be noted borhood of 1% tetraethylenepentamine and 99% propylene oxide.

Ewample F The entire yield of the previous example, Example E, to wit, 1022 grams, were treated with 2 moles-of propylene oxide (11'6" grams) without addition. of any more catalyst. The operatingconditions were the same as before except thatthe time was: comparatively shorter, being about 20 minutes, due to the small amount of propylene oxide added.

In the; final, product the molal ratio was approximately 311 to 1, and the amine represented about 1% of; the final. product. assuming- COl'fliplete reaction. All the various products obtained from polyamines or their derivatives, gave liquids varying from those having a viscosity inv some instance castor oil or blownoastor oil; down to? glycerol or polypropylene glycol, or the like. The color varied from a; deep reddish amber to alight amber, or pale reddish straw color. Color seemed to beidue to the nitrogenous compounds, or a trace of decomposition products, orpossibly 10 a. trace of metal obtained from the reaction vessel. These products can be decolorized' in the usual way with charcoal, clay, or the like. When exposed to sunlight they seem todarken again. For most purposes herein described and particu larly as demulsifiers, such color is not significant and no particular attempt was made to control.

color.

Example G The same procedure: was employed as in the six examples preceding, but triethyl'enetetramine was substituted for tetraethylenepentamine. The operating conditions were substantially the same and the same molalratios and same allocable proportions were taken-at each'stage.

The resultant products-were all similar to thoseobtained in Examples A to F, preceding, and water-insolubility seemed to appear in molecular weight range of 5,000 or thereabouts. On-the emulsions.previously referred to obtained from."

the vicinity of Beaumont, Texas, these particular products were not quite as good as those derived from tetraethylenepentamine.

It: will be noted that some of the reactants: referred to in the subsequent tables of further examples wereobtained by'reaotion of glycide' on selected polyamino reactantsl- Attention is, directed to the fact that the use of glycide requires extreme caution. This is particularly true on any scale other than small laboratory or semipilot plant operations. Purely from the standpoint of safety in the handling of glycide, attention is directed to the following: (a) If prepared from glycerol monochlorohydrin this product should be comparatively pure; (2)) the glycideitself should be as pure as possible, as the clients of impurities are difilcult to evaluate; (c) the glycide should be introduced'careiuliy and precaution should be taken that it reacts as promptly as introduced, i. e., that no excess of glycide is allowed to accumulate; (d) all necessary precaution shouldv be taken that glycide cannot polymerize per se; (6) due to the high boiling point of glyoid'e one can readily employ a typical separatable glass-resin pot as described in the co-pending application of Melvin De Grooteand Bernhard Keiser, Serial No. 82,704, filed March 21, 1949' (now Patent No. 2,499,370, dated March 7, 1950), and offered for sale by numerous laboratory supply houses. If such arrangement is used to prepare laboratory scale duplications, then care should be taken that the heating mantle can be removed rapidly so as to allow for cooling; or better still, through an add ed opening at the top of the glass resin pot or comparable vessel should be equipped with a stainless steel cooling coil so that the pot can be cooled more. rapidly than mere removal of mantle. If a stainless steel coil is introduced it means that conventional stirrer of the paddle type is changed into the centrifugal type which causes the, fluid; or reactants to due to swirling action in, the center'ofthe pot. Still better, is the use of a laboratory autoclave of the kind previously described in this section; but in any event, when the initial amount-of glyoide is added to a suitable reactant, the speed of reaction should be controlled by theusual factors, such as (a) the rate: of additionoi glycide; (b) the elimination of? external heatLand-L (0) use of cooling coil so there-is no undue-rise-ih temperature. All the foregoing is merely conventional but is included due to the hazard in handling glycide.

TABLE 1 Amt. of Amt. of Molal Ratlo No. of Propyl- Molec g Polyhydric Chemical Compound, or Prior Molec. Reactive Amt. ggi ene g figgg ggg g Wt. of e Derivative Wt. Hydrogen gms. Add a Oxide i 1 H d Deriva- Atoms 9 Added e y tive if any gms Atom HB Polyamine 1 275 9 20:1 2.2 1, 435 Monoglycerol ether of tetraethylenepentaminc 2 263 8 20: 1 2. 1, 423 Diglycerol ether of tetraethylenepentamine L 337 9 20:1 2. 2 1, 497 Triglycerol ether of tetracthylenepentamine 4 411 20:1 2.0 1, 571 Monoglycerol ether of HB amine 5 349 10 20:1 2.0 1, 509 Diglycerol ether of HB amine 423 11 20:1 1. 9 1, 583 Triglycerol ether of HB amine 1 497 12 20:1 1. 8 1, 657 Monoethyleneglyool ether of Tetraethylcne pentamine 5 233 7 20:1 3 1, 393 Diethyleneglycolether of Tetraethylene pentamine 277 7 20:1 3 1, 437 Hydroxycthyl ethylcnediamine. 104 4 20:1 5 1, 264 Propylene diamine A 74 4 20:1 5 1, 234 Dipropylene triamine. 131 5 20:1 4 1, 291

Monoacetyl derivative of Tetraethylene pentamine 231 6 231 do 1,160 20:1 3.3 1,391 14 Reaction product of propylene diamine (1 mole) and ethylene imine (2 moles) 150 6 150 do 1,160 20:1 3.3 1,310 Reaction product of dipropylenc triamine (1 mole) and ethylene imine (2 moles) -1 217 7 217 -do 1, 160 :1 3 1,377 16 Reaction product of tetraethylene pentamine (1 mole) and ethylene imine (5 moles) 404 12 404 do..-" 1, 160 20:1 1.8 1, 564

1 HB amine is the trade name for a high boiling polyamine residue remaining after the distillation of tetraethylenepentamine. It is undoubtedly a mixture of the immediately higher homologues of tetraethylenepentamme, and the above value of 275 molecular weight is an approximation corresponding roughly to hexaethylene heptamine.

2 Obtained by reaction of one mole of glycide and one mole of tetraethylenepentamine.

a Obtained by reaction between 2 moles of glycide and one mole of tetraethylenepentamine.

4 Obtained by reaction between 3 moles of glycide and one mole of tetraethylenepentamine.

Obtained from high boiling polyamine previously described and glyclde in equal molar ratio.

9 Obtained from high boiling polyamine (1 mole) and glyeide (2 moles).

7 Obtained from high boiling polyamine (1 mole) and glycide (3 moles).

* Obtained by reacting one mole of ethylene oxide with one mole of tetraethylenepentamine.

' Obtained by reacting one mole of tetraethylenepentamine with 2 moles of ethylene oxide.

TABLE 2 Polyhydric Amt. of

(hemical Melee gkg g Amt ai fig Propylene Molal Ratio Molec. Example No. Compound Oxide per Initial Wt. of De Dor Prior igggg gg gg Added, Molecule rivative erivative gms.

TABLE 3 Polyhydric No. of Amt. of

Chemical Melee Reactive Amt s 5, 1 Propylene Molal Ratio -y Water Example No. Compound Hydroo e Oxide per Initial tic Soluor Prior gen Added If Added, Molecule D bility Derivative Atoms g'ms.

17 3, 755 9 751 15 580 9011 6, 655 N0 18 3, 743 8 748 15 580 9021 6, 643 N 0 19 3, 817 9 765 15 580 9011 6, 717 N0 20 3, 891 10 778 15 580 9021 6, 791 N 0 21 3, 829 10 766 15 580 90 :1 6, 729 N0 22 3, 903 11 781 15 580 9011 6, 803 N0 23 3, 977 12 795 15 580 9011 6, 877 N0 24 3, 713 7 745 15 580 90 21 6 613 N0 25 3, 7 7 751 15 580 9021 6, 657 N0 26 3, 584 4 717 15 580 9011 6, 484 NO 27 3, 554 4 711 15 580 9021 6, 454 N0 28 3, 611 5 722 15 580 9021 6, 511 N0 29 3, 711 6 742 15 580 9021 6, 611 NO 30 3, 630 6 726 15 580 9021 6, 530 N O 31 3, 797 7 759 15 580 9011 6, 697 N0 32 3, 884 12 777 15 580 9011 6, 784 N0 TAB-LE 4 -Polyhydric No. of Amt. of 1 Chemical M0166 Reactive Amt a ai Propylene Molal Ratio g Water Example No., Compound Wt Hydro- Aded if Oxide per Initial i Soluor Prior gen g Added, Molecule bility Derivative Atoms gms.

33 6, 655 9 58(1- 140:1 9, 555 N 34 6, 643 8 580 140:1 9, 543' N0 35. 6, 717' 9- 580 140:1 9, 617 N0 36 6, 791 580' 140:1 9, 691 N0 37 6, 729 10 5S0v 140:1 9, 629 No 38 6. 803 11 580- 140:1 9, 703 No 39 6,877 12 580 140:1 9,777 No 40 6, 613 7 580 140:1 9, 513 NO 41 6.557 7 5801 140:1 9, 557 N0 42 6, 484 4 580 140:1 9, 384 No 43 6, 454 4- 580 1'40 1 9,354 No 44- 6, 511 5 V 580 140 :1. 9,.411 No 45 6,611 6 580 140:1 9, 511 No 46 6, 530 6 580 140:1 9, 430 N 0 47: 6, 697- 7 580 140:1. 9, 597 N0 48 6, 784 12 v580 140:1 9, 684 No TABLE 5 Polyhydric No; of Amt. of l Chemical M0190 Reactive Amt g zi f Propylen Molal Ratio l gg g Water ExampleNo. Compound, Hydro- I" Add Oxide per 'Initlal fi Soluor Prior gen 1 Added, Molecule bility Derivative Atoms ems. atwe 49 9, 555 i 9 I 1, 911 5' Y 580 190:1 12, 455 N0 50 9; 543: 8 1, 908: 5 580* 190:1 12, 443 N0 51 9, 617 9, l, 925 5 580 190:1 12, 517 No 52 9; 691; 10 1,933 5 580 1.90:1 1'2, 591 N0 53 9, 629 10 1,926 5 l 580 190:1 12, 529 N0- 54 9, 703 ll 1, 941 5 580 190:1 12, 603 N0: 55 9,- 777 Y 12' 1, 955 5 580 190:1 12, 677' No 56 9,513 1 7- 1, 905- 5 580 190:1 12,413 N0 57 9, 557 7 1, 911 5; 580 190: 1 12, 457 N0 58- 9,384 4 1, 877 5 i 580' 19021 12, 284 No 59 9,354. 4 1,871 5: 5802- 190:1 12,254 No 60 9, 411 5 1, 882 5' 580 190:1 12, 311 N0 61 9, 511 6 1,902 5 580 190:1 12,411 No 62 9,430 6 l, 886 5 580- 190:1 12, 330 N0 63* 9, 597' 7 1, 919 5 580 190:1 12,497 No l 64 9;,684. 12 1,937 5 580 190:1 12, 584 N0 In order to illustrate why the hereinspecified compounds orv products are ccgeneric mixtures and notsingle chemical compounds and why they must, be described in terms of manufacture and molal ratio or percentage of' reactants, reference is made to a. monohydric alcohol or a secondary amine having a, single reactive aminohydrogen atom. Needless to say, after the first mole of propylene oxide reacts with such amine the aminohydrogen atom is replaced by an alkanol radical. One of the simplest compounds herein contemplated as an initial reactant is ethylenediamine or hydroxyethyl ethylenediamine. In either. instancethere are at least 4 reactive hydrogen atoms. Other examples appearing elsewhere herein. may have a dozen or more reactive hydrogen atomsas in the case; of a mole of tetraethylenepentamine which. has. been treated with 7. moles of glycide. However, one need only consider what happens when a monohydric alcohol issubj ected to oxyalkylation.

If, one selects any hydroxylated compound and subjects such compound to oxyalkylation, such oxyethylation or oxyp-ropylation, it becomes obvious that one is. really producing a. olymerof the alkylene oxide except for the terminal group. This is particularly true wherevt he amount of oxide added is, comparatively large, for instance, 10,. 20, 30, 40,. or 50 units. If such a compound is subjected to oxyethylation so as to introduce 30 units of ethylene oxide it is well known that one does not obtain a single constituent which, for sake of convenience may be indicated as ROGCzHrOhoH. Instead, one obtains. a cogeneric mixture of closely related homologues in which. the formula may be shown as the following: RO-(-C2HiO).nH, wherein n, as

far as. the statistical average goes, is 30, but: the individual members present in significant amount may vary from instances where n has a. value of 25. and perhaps less, to a point where 11. may represent or more. Such mixture is, as stated, a cogeneric closely related series of touching homologpus: compounds. Considerable investigation has been made in regard to the distribution curves for linear polymers. Attention is directed tov the article entitled. Fundamental Principles.

of Condensation Polymerization, by Paul J Flory, which appeared in Chemical Reviews, volume 39, No... 1, page 137'.

Unfortunately, as has. been pointed out by Flory and, other investigators, there is no satisfactory method, based on either experimental or. mathematical examination,. of indicating the exact proportion of the various members oi touching homologous series which appear in cogeneric condensation. products of the. kind described. This means that from the practical standpoint, i. e., the ability to describe how to make the product under consideration and how to repeat such production time after time without d-ifiiculty, it is necessary to resort to some other: method of description.

What has been said in regard toa monohydric' compound, of course, is multiplied many, many times in the; case of a tetrahydric compound and.

a. hexahydric compound, or one having even a, larger number of hydroxyls. This is particularly true when enough propylene oxide is added to ive, at least on a statistical basis, assuming. complete reaction, a compound having a molecular weight within the range previously specified;

- Basically, the compounds herein described OWE5 their peculiar properties to a number of factors previously enumerated, at least in part: (a) size of molecule; (b) shape of molecule as far as space configuration goes; absence of a single hydrophobe group having as many as 8 uninterrupted carbon atoms in a single radical; (11) substantial insolubility in water; and (e) such combination being obtained by the action of propylene oxide alone for all practical purposes.

Actually it can be seen that certain variations could be made without detracting from the spirit of the invention as, for example, one could start with a material such as tetraethylenepentamine and treat this polyamine with approximately 50 moles of propylene oxide and then with 7 moles of glycide, and then with another 50 moles of propylene oxide. Actually, if 7 moles of glycide went on at the end of the intermediate structure and oxypropylation has resulted, the only thing that would happen is that there would be 14 terminal groups instead of 7. If one started with triethylenetetramine and followed the same procedure there would be 12 instead of 6' terminal groups.

Actually, the introduction or interruption of a propylene oxide chain by a glycide radical obviously does not depart from this invention and is included within the expression oxypropylation for reasons which require no further explanation. The same thing is true if at some stage in oxypropylation one injected one or two ethylene radicals which would not offset other factors which complete the overall structure, such as molecular size, insolubility in water, etc. If one used a mole of butylene oxide for each polyamine again one would get the same effect for the reason that the overall picture has not been changed and there is no departure from the spirit of the invention. For that matter, one might use a few moles of ethylene oxide and a few moles of butylene oxide.

Basically, a comparatively simple low molal water-soluble polyamine of the kind specified is transformed into a high molal water-insoluble compound having a molecular weight of several thousand up to 25,000 or 30,000, and such insolubility is brought about substantially by the use of propylene oxide alone. The preferred range of molecular weight is in the neighborhood of 4,000 or thereabouts, to 14,000 or thereabouts.

It is to be noted that somewhat analogous products can be derived from other amines, either monoamines or polyamines. For instance, monoamines such as triethanolamine, tripropanolamine, tributanolamine, or the like, can be treated with propylene oxide as such, or such amines can be reacted first with glycide so as to increase the number of reactive hydrogen atoms and then treated with propylene oxide.

Another class of amines are those in which the carbon atom chain linkin two or more nitrogen atoms is invariably interrupted by an oxygen atom. Examples of such amines are those obtained by the action of dichloroethylether on ammonia, or other amines in the same manner as when ethylene dichloride is used. The amines so produced, of course, show the typical oxygen interrupted carbon atom chain between the nitrogen atoms. Other similar compounds are obtained by heating triethanolamine, tripropanolamine, tributanolamine, or the like, so as to form ether linkages. Such amines can, of course, be treated with alkylene oxides, and then caused to etherize so as to lengthen the chain between the nitrogen atoms. Similar amines are obtained by the action of ethylene imine on hydroxylated compounds such as glycerol, diglycerol, etc. In-

other instances polyamines may show both types of linkages, (a) carbon atom chains without interruption by oxygen atoms, and (12) carbon atom chains interrupted by oxygen atoms. For

instance, ethylenediamine, triethylenetetramine,

or tetraethylenepentamine may be treated with ethylene oxide, or some other alkylene oxide,.and then heated so as to cause ether formation. These compounds illustrate products having both types of linkages. Needless to say, from all these various amines one can prepare the same derivatives which bear a simple genetic relationship to the original amine except those pointed out inthe earlier text of the instant invention. ,7

It is desired to emphasize the fact that the instant invention is limited to a comparatively narrow range of materials which must have at least two or more nitrogen atoms, of which at least one must be basic; such nitrogen atoms must be 4 time the three most desirable initial. reagents are tetraethylenepentamine, pentaethylenehexamine, and hexaethyleneheptamine. The last two of these are best available as constituents of the high boiling polyethyleneamine residue previously referred to.

However, without any reservation as to immediate availability in the open market I would select the same higher alkylene polyamines which had been treated with glycide in the ratio of at least one mole of glycide per reactive hydrogen, as

an outstanding reactant for combination with propylene oxide. In fact, such xypropylated derivatives are so outstanding that they represent an invention within an invention.

PART 3 Conventional demulsifying agents employed in the treatment of oil field emulsions are used as such, or after dilution with any suitable solvent,

- such as water, petroleum hydrocarbons, suchas benzene, toluene, xylene, tar acid oil, cresol, anthracene oil, etc. Alcohols, particularly aliphatic alcohols, such as methyl alcohol, ethyl alcohol,

denatured alcohol, propyl alcohol, butyl alcohol,

hexyl alcohol, octyl alcohol, etc., may be employed as diluents. Miscellaneous solvents, such as pine oil, carbon tetrachloride, sulfur dioxide extract obtained in the refining of petroleum, etc., may be employed as diluents. Similarly, the material or materials employed as the demulsifying agents of my process may be admixed with one or more of the solvents customarily used in connection with or in an oil-soluble form, or in a form exhibiting both 011- and water-solubility. Sometimes they may be used in a form which exhibits relatively.

limited oil-solubility. However, since such re agents arefrequently-used-inaratio of 1 to'1'0',0( )0 or 1 to 203000, or 1 to30,000,-or even -1 to l0,000, or '1 to 50,000; as in desalting practice, such an apparent insolubility in oiland water is not significant because-said reagents undoubtedly have solubility within such concentrations. This same :factis true in regard to thematerialor materials employed as the 'demulsifying agent of my process.

In practicing my process for resolving petroleum emulsions of the water-in-oil type, a treating agent or demulsifying agent of the kind above described is brought intocontact with or caused toact upon the emulsion to be treated, inany of the various apparatus now generally used to resolve or break petroleum emulsions with a chemical reagent, the above procedure being used alone or .in combination with other demulsifying procedure, such as the electrical dehydration process.

One type of procedure is to accumulate a volume of emulsified oil in a tank and conduct a batch treatment-type of demulsification procedure to recover clean oil. .In this procedure the emulsion is admixed with the demulsifier, for example, by agitating the tank of emulsion and slowly'dripping demulsifier into the emulsion. In some-cases mixingis .achieved .by heating the emulsion while dripping in the demulsifier, depending upon the convection currents in the emulsion to produce satisfactory admixture. In a third modification of this type of treatment, a circulating pump withdrawsemulsionirom,egl, the bottom of the tank, and re-introduces .it into the top of the tank, the .demulsifierbeing added, for example, at the suction sideof said circulating pump.

In a second type of treating procedure, the demulsifier is introduced into the Well fluids at the well-head or at some point between the wellhead and the final oil storage tank, by means of an adjustable proportioning mechanism or proportioning pump. Ordinarily the flow of fluids through the subsequent lines and. fittings suffices to produce the desired degree of mixing .of demulsifler and emulsion, although in some instances additional mixing devicesjmay be introduced into the flow system. In this general procedure, the system may include various mechanical devices for withdrawingfree .water, separating entrained Water, .or accomplishing .quiescent settling of the chemicalized emulsion. Heating devices may likewise be incorporated in any of the treating procedures described herein.

A third type of application (down-the-hole) of demulsifier to emulsion is to introduce the demulsifier either periodically or continuously in diluted or undiluted form into the well and to allow it to come to the surface with the well fluids, and then to flow the chemicalized emulsion through any desirable surface equipment, such as employed in the other treating procedures. This particular type of application is decidedly useful when the demulsifier is used in connection with acidification of calcareous oil-bearing strata, especially if suspended in or dissolved in the acid employed for acidification.

In all cases, it will be apparent from the foregoing description, the broad process consists simply in introducing a relatively small proportion of demulsizier into a relatively large proportion of emulsion, admixing the chemical and emulsion either through natural flow or through special apparatus, with or without the applica- 'tion of'heat' and allowing the mixture to stand quiescent until the undesirable water content of the emulsionseparates and settles from the mass.

The following is a typical installation: 1 A reservoir-to hold thedemul'sifi'er of the kind described (diluted or undiluted) is placed at the well-head where the efiluent liquids leave the well. This reservoir or container, which may vary from 5 gallons to 50 gallons for convenience, is connected to a proportioning pump which in jects the demulsifler drop-wise into the fluids leaving the well. Such chemicalized fluids pass through the flowline into a settling tank. The settling tank consists of a tank of any convenient size, for instance, one which will hold amounts of fluid produced in 4 to 24 hours (500 barrels to '2000 barrels capacity), and in which there is a perpendicular conduit from the top of the tank to almost the very bottom so as to permit the incoming fluids to pass from the top of the settling tank to the bottom, so that such incoming fluids do not disturb stratification which takes place during the course of demulsification. The settling tank has two outlets, one being below the water level to drain oil the water resulting from demulsification or accompanying the emulsion as free water, the other bein an oil outlet at the top to permit the passage of dehydrated oil to a second tank, being a storage tank, which holds pipeline oil or dehydrated oil. If desired, the conduit or pipe which serves to carry the fluids from the well to the settling tank may include a section of pipe with bafilesto serve as a mixer, to insure thorough distribution of the demulsifier throughout the fluids, or a heater for raising the temperature of the fluids to some convenient temperature, for instance, 120 to 160 F., or both heater and mixer.

Demulsification procedure is started by simply setting the pump so as to feed a comparatively large ratio of demulsifier, for instance, 1:5,000. As soon 'as a complete break or satisfactory demulsification is obtained, the pump is regulated until experience shows that the amount of demulsifier being added is just suflicient to produce clean or dehydrated oil. The amount being fed at such stage is usually 1:10,000, 1215,000, 1120,000, or the like. V

In many instances the oxyalkylated products herein specified as demulsifiers can be conveniently used without dilution. However, as previously noted, they may be diluted as desired with any suitable solvent. For instance, by mixing '75 parts by Weight of an oxyalkylated derivative, for example, the product of Example C, with 15 parts by weight of xylene and 10 parts by weight of isopropyl alcohol, an excellent demulsifier is obtained. Selection of the solvent will vary, depending upon the solubility characteristics of the oxyalkylated product, and of course will be dictated in part by economic considerations, i. e., cost.

As noted above, the products herein described may be used not only in diluted form, but also may be used admixed with some other chemical demulsifier. For example, a mixture which exemplifies such combination is the following:

Oxypropylated derivative, for example, the product described as Example C, 30%;

A cyclohexylamine salt of a polypropylated naphthalene monosulfonic acid, 20%;

An oil-soluble petroleum sulfonic acid sodium salt, 20%;

Isobutyl alcohol, 5%;

High boiling aromatic solvent, 25%.

The above proportions are all weight per cents.

Having thus described my invention, what I claim as new and desire to secure by Letters Patent, is:

1. A process for breaking petroleum emulsions 01 the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including high molal oxypropylation derivatives of monomeric polyamino compounds, with the proviso that (a) the initial polyamino reactant be free from any radical having at least 8 uninterrupted carbon atoms; (b) the initial polyamino reactant have a molecular weight of not over 1800 and at least a plurality of reactive hydrogen atoms; the initial polyamino reactant must be water-soluble; (d) the oxypropylation end product must be water-insoluble; (e) the oxypropylation end product be within the molecular weight range of 2000 to 30,000 on an average statistical basis; (I) the solubility characteristics of the oxypropylation end product in respect to water must be substantially the result of the oxypropylation step; (9) the ratio of propylene oxide per initial reactive hydrogen atom must be within the range of 7 to 70; (h) the initial poly amino reactant must represent not more than by weight of the oxypropylation end product on a statistical basis; (1') the preceding provisos are based on the assumption of complete reaction involving the propylene oxide and initial polyamino reactant; (5') the polyamino reactant must contain at least one basic nitrogen atom; and (k) the nitrogen atoms are linked by a carbon atom chain.

2. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including high molal oxypropylation derivatives of monomeric polyamino compounds, with the proviso that (a) the initial polyamino reactant be free from any radical having at least 8 uninterrupted carbon atoms; (1)) the initial polyamino reactant have a molecular weight of not over 1800 and at least a plurality of reactive hydrogen atoms; (0) the initial polyamino reactant must be water-soluble; (d) the oxypropylation end product must be water-insoluble; (e) the oxypropylation end product be within the molecular weight range of 2000 to 30,000 on an average statistical basis; (f) the solubility characteristics of the oxypropylation end product in respect to water must be substantially the result of the oxypropylation step; (g) the ratio of propylene oxide per initial reactive hydrogen atom must be within the range of 7 to (h) the initial polyamino reactant must represent not more than 20% by weight of the oxypropylation end product on a statistical basis; (2') the preceding provisos are based on the assumption of complete reaction involving the propylene oxide and initial polyamino reactant; (7') the polyamino reactant must contain at least a plurality of basic nitrogen atoms; and (k) the nitrogen atoms are linked by a carbon atom chain.

3. The process of claim 2 with the proviso that the polyamino compoundbe a polyalkylene amino compound.

4. The process of claim 2 with the proviso that the polyamino compound be a polyethylene amino compound.

5. The process of claim 2 with the proviso that the polyamino compound be a polyethylene amino compound, and with the further proviso that the molecular weight range be within the ratio of 4,000 to 10,000.

6. The process of claim 2 with the proviso that the polyamino compound is triethylenetetramine, and with the further proviso that the molecular weight range be within the ratio of 4,000 t 10,000.

7. The process of claim 2 with the proviso that the polyamino compound is tetraethylenepentamine, and with the further proviso that the molecular weight range be within the ratio of 4,000 to 10,000. I

8. The process of claim 2 with the proviso that the polyamino compound is a high boiling resid ual polyethylene amino compound having more than 5 nitrogen atoms per molecule, and with the further proviso that the molecular weight range be within the ratio of 4,000 to 10,000.

MELVIN DE GROOTE.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,233,383 De Groote et al. Feb. 25, 1941 2,243,329 De Groote et a1. May 27, 1941 2,262,358 De Groote et a]. Nov. 11, 1941 2,262,736 De Groote et a1. Nov. 11, 1941 2,262,743 De Groote et a1. Nov. 11, 1941 2,290,154 Blair July 21, 1942 

1. A PROCESS FOR BREAKING PETROLEUM EMULSIONS OF THE WATER-IN-OIL TYPE CHARACTERIZED BY SUBJECTING THE EMULSION TO THE ACTION OF A DEMULSIFIER INCLUDING HIGH MOLAL OXYPROPYLATION DERIVATIVES OF MONOMERIC POLYAMINO COMPOUNDS, WITH THE PROVISO THAT (A) THE INITIAL POLYAMINO REACTANT BE FREE FROM ANY RADICAL HAVING AT LEAST 8 UNINTERRUPTED CARBON ATOMS; (B) THE INITIAL POLYAMINO REACTANT HAVE A MOLECULAR WEIGHT OF NOT OVER 1800 AND AT LEAST A PLURALITY OF REACTIVE HYDROGEN ATOMS; (C) THE INITIAL POLYAMINO REACTANT MUST BE WATER-SOLUBLE; (D) THE OXYPROPYLATION END PRODUCT MUST BE WATER-INSOLUBLE; (E) THE OXYPROPYLATION END PRODUCT BE WITHIN THE MOLECULAR WEIGHT RANGE OF 2000 TO 30,000 ON AN AVERAGE STATISTICAL BASIS; (F) THE SOLUBILITY CHARACTERISTICS OF THE OXYPROPYLATION END PRODUCT IN RESPECT TO WATER MUST BE SUBSTANTIALLY THE RESULT OF THE OXYPROPYLATION STEP; (G) THE RATIO OF PROPYLENE OXIDE PER INITIAL REACTIVE HYDROGEN ATOM MUST BE WITHIN THE RANGE OF 7 TO 70; (H) THE INITIAL POLYAMINO REACTANT MUST REPRESENT NOT MORE THAN 20% BY WEIGHT OF THE OXYPROPYLATION END PRODUCT ON A STATISTICAL BASIS; (I) THE PRECEDING PROVISOS ARE BASED ON THE ASSUMPTION OF COMPLETE REACTION INVOLVING THE PROPYLENE OXIDE AND INITIAL POLYAMINO REACTANT; (J) THE POLYAMINO REACTANT MUST CONTAIN AT LEAST ONE BASIC NITROGEN ATOM; AND (K) THE NITROGEN ATOMS ARE LINKED BY A CARBON ATOM CHAIN. 